CN105431489A

CN105431489A - Carbon material dispersed film formation composition

Info

Publication number: CN105431489A
Application number: CN201480042831.3A
Authority: CN
Inventors: 鹿内康史; 西村直也; 小泽雅昭
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-07-31
Filing date: 2014-07-31
Publication date: 2016-03-23
Anticipated expiration: 2034-07-31
Also published as: EP3029111A1; US20160160079A1; CN105431489B; WO2015016316A1; JP6465024B2; EP3029111A4; JPWO2015016316A1

Abstract

A carbon material dispersed film formation composition including: a polymer that includes a triazine ring-containing repeating unit structure, such as that represented by formula (17) for example; a cross-linking agent; and a carbon material. The carbon material is well dispersed in the composition, and therefore by using this composition, a cured film in which the carbon material is well dispersed can be produced.

Description

Carbon material dispersion membrane formation composition

Technical field

The present invention relates to carbon material dispersion membrane formation composition.

Background technology

Carbon nanotube (being hereafter sometimes also abbreviated as CNT) as the useful materials of nanotechnology, the just studied possibility applied in wide spectrum.

As its purposes, the method being roughly divided into the independent CNT of use that such as transistor, microscope probe etc. are such itself and the electrode such as discharging electronics or electrode for fuel cell or the conductive composite body that CNT is disperseed, ink, coating etc. such many CNT are put together the method used as aggregate (bulk).

When using independent CNT, adopting and CNT is joined in solvent, after irradiating ultrasonic wave to it, by methods etc. that the CNT of single dispersion is taken out such as electrophoresis.

On the other hand, for the conductive composite body used by aggregate, in the middle of the polymkeric substance etc. that CNT must be made to be distributed to well as substrate material.

But CNT generally not easily disperses, for the complex body adopting common dispersion means to obtain, its dispersion becomes incomplete state.Therefore, people are studying and are adopting the various method such as surfaction, surface chemical modification of CNT dispersed to improve it.

Such as, one of method of disperseing as making CNT, someone proposes poly-((the m-phenylene 1 making to have coil structure, 2-vinylidene)-co-(two octyloxies-p-phenylene vinylene)) be attached to method (patent documentation 1) in CNT surface.

In the document, although can CNT be made in organic solvent to disperse isolatedly, demonstrate polymkeric substance and be attached to appearance on 1 CNT, but for the method for the document, once make it be dispersed to a certain degree trap CNT by condensing and precipitating again, just CNT can not be preserved for a long time with the state of isolated dissolving.

On the other hand, also someone proposes to be conceived to the method (patent documentation 2) of high branched-chain polymer as the dispersion agent of CNT.So-called high branched-chain polymer refer to as star polymer, dendritic (dendroid) polymkeric substance be classified as such as branch-shape polymer and hyperbranched (hyperbranchedpolymers) polymkeric substance etc. such, the polymkeric substance in skeleton with side chain.

These high branched-chain polymers are owing to introducing side chain energetically, there is so-called more sparse internal space or the special shape of corpuscular property, modifiable multiple end is made it have by introducing various functional group, utilize these features, make it can by CNT high dispersing compared with the straight-chain polymer of cord shape.

But, according to the above-mentioned high branched-chain polymer of use as the technology of the patent documentation 2 of dispersion agent, in order to keep the isolated dispersion state of CNT for a long time, except mechanical treatment, also must heat-treat, and not more high better to the dispersive ability of CNT.

On the other hand, containing the hyperbranched polymer of repeating unit with triazine ring and aromatic nucleus, it is excellent to the dispersing and dissolving ability of carbon nanotube, when using this high branched-chain polymer agent solvable as the dispersion of carbon nanotube, being dissolved to its individual size becoming isolated for carbon nanotube (at least partially) possible (patent documentation 3).

In addition, when the high branched-chain polymer that will comprise triarylamine compounds, aldehyde cpd and/or ketone compound uses as the solvable agent of dispersion of carbon nanotube, carbon nanotube (at least partially) can be made to isolate and to be dissolved to its individual size, by using these dispersion liquids and urea system (uril-type) linking agent, can obtain homodisperse for CNT heat cured film (patent documentation 4).

, in recent years, at making liquid-crystal display, organic electroluminescent (EL) indicating meter, touch-screen, photosemiconductor (LED) element, solid-state imager, organic thin film solar cell, dye-sensitized solar cell, OTFT (TFT), lens, prism, photographic camera, binocular, microscope, parts during semiconductor exposure device etc. etc. are in the field of electron device or optical material, require to use curable film formation composition, but for containing the hyperbranched polymer of repeating unit with triazine ring and aromatic nucleus, conduct a research not yet in this respect so far.

Prior art document

Patent documentation

Patent documentation 1: JP 2000-44216 publication

Patent documentation 2: No. 2008/139839th, International Publication

Patent documentation 3: No. 2010/128660th, International Publication

Patent documentation 4: No. 2011/065395th, International Publication

Summary of the invention

Invent problem to be solved

The present invention carries out in view of such situation, and object is to provide a class carbon material dispersion membrane formation composition, and said composition can make carbon material be dispersed in well wherein, meanwhile, can form the cured film of the state of carbon material good distribution.

For solving the means of problem

The present inventor etc. study intensively in order to achieve the above object and repeatedly, found that, the film formation composition of the polymkeric substance containing triazine ring containing regulation, linking agent and carbon material, not only carbon material disperses in the composition well, even and if the cured film that carbon material still can disperse well after film formation can be formed, thus complete the present invention.

That is, the invention provides:

1, carbon material dispersion membrane formation composition, is characterized in that, wherein comprises the polymkeric substance containing triazine ring containing the repeat unit structure represented by following formula (1), linking agent and carbon material:

[changing 1]

In formula, R and R ' represents hydrogen atom, alkyl, alkoxyl group, aryl or aralkyl independently of each other; Ar represents at least a kind in the group selecting free style (2) ~ (13) to represent;

[changing 2]

In formula, R ¹~ R ⁹²represent the alkoxyl group of the alkyl of the had branched structure of hydrogen atom, halogen atom, carboxyl, sulfo group, carbon number 1 ~ 10 or the had branched structure of carbon number 1 ~ 10 independently of each other; R ⁹³and R ⁹⁴represent the alkyl of the had branched structure of hydrogen atom or carbon number 1 ~ 10; W ¹and W ²represent singly-bound, CR independently of each other ⁹⁵r ⁹⁶(R ⁹⁵and R ⁹⁶represent the alkyl (wherein, they also can form ring together) of the had branched structure of hydrogen atom or carbon number 1 ~ 10 independently of each other), C=O, O, S, SO, SO ₂, or NR ⁹⁷(R ⁹⁷represent the alkyl of the had branched structure of hydrogen atom or carbon number 1 ~ 10); X ¹and X ²the alkylidene group representing the had branched structure of singly-bound, carbon number 1 ~ 10 independently of each other or the group represented by formula (14):

[changing 3]

In formula, R ⁹⁸~ R ¹⁰¹represent the alkoxyl group of the alkyl of the had branched structure of hydrogen atom, halogen atom, carboxyl, sulfo group, carbon number 1 ~ 10 or the had branched structure of carbon number 1 ~ 10 independently of each other; Y ¹and Y ²represent the alkylidene group of the had branched structure of singly-bound or carbon number 1 ~ 10 independently of each other;

2, the carbon material dispersion membrane formation composition described in 1, wherein, above-mentioned carbon material contains at least a kind that is selected from carbon nanotube, carbon nanohorn (carbonnanohorns), soccerballene, Graphene, carbon black, section's qin carbon black, graphite and carbon fiber;

3, the carbon material dispersion membrane formation composition described in 1, wherein, above-mentioned carbon material contains carbon nanotube, and this carbon nanotube is isolated is dispersed to individual size;

4, the carbon material dispersion membrane formation composition described in 1, wherein, above-mentioned carbon material is carbon black;

5, the carbon material dispersion membrane formation composition described in any one of 1 ~ 4, wherein, above-mentioned linking agent is the compound of photocurable and/or thermofixation;

6, the carbon material dispersion membrane formation composition described in any one of 1 ~ 4, wherein, above-mentioned linking agent is be selected from least a kind in multifunctional (methyl) acrylic compounds, multi-functional epoxy compound and polyfunctional isocyanate compound;

7, cured film, it is for obtaining by making carbon material dispersion membrane formation composition described in any one of 1 ~ 6 solidify;

8, electron device, it cured film described in 7 possessing base material and formed on the substrate;

9, optical material, it cured film described in 7 possessing base material and formed on the substrate.

The effect of invention

Carbon material dispersion membrane formation composition of the present invention is due to the polymkeric substance (hyperbranched polymer) containing triazine ring containing regulation, therefore make, be that the carbon material of representative disperses in the composition well with CNT, particularly when CNT, the isolated dissolving (dispersion) of CNT can be made to its individual size.

Carbon material dispersion membrane formation composition of the present invention is due to containing polymkeric substance, linking agent and carbon material containing triazine ring as described above, therefore, by using said composition, even if the cured film that carbon material after film formation still can disperse well can be formed.Especially, the polymkeric substance containing triazine ring used in the present invention is due to two kinds of performances of the dispersion agent and tackiness agent simultaneously with carbon materials such as CNT, can under the condition not reducing carbon material dispersiveness hydridization, therefore, can make and not only can make the uniform cured film of carbon material high dispersive (being isolated dispersion when CNT) containing carbon material in a large number.

This cured film is owing to containing the crosslinked polymkeric substance containing triazine ring and carbon material, therefore, can give play to by the high heat resistance brought containing the polymkeric substance of triazine ring be cross-linked, high refractive index, the characteristics such as low volumetric shrinkage, simultaneously, the electroconductibility brought by carbon material can also have been given play to, the characteristics such as opacifying property, anti-inner face reflection, control the functions such as transmitance, therefore, go for making liquid-crystal display, organic electroluminescent (EL) indicating meter, touch-screen, photosemiconductor (LED) element, solid-state imager, organic thin film solar cell, dye-sensitized solar cell, OTFT (TFT), lens, prism, photographic camera, binocular, microscope, parts during semiconductor exposure device etc. etc. are in the field of electron device or optical material, or in the field of the decoration coating of various parts surfaces etc. or ink.

Accompanying drawing explanation

Fig. 1 in synthesis example 1 obtain macromolecular compound [3] ¹h-NMR spectrogram.

Fig. 2 for illustrate in synthesis example 1 obtain the figure of the TG-DTA measurement result of macromolecular compound [3].

Fig. 3 in preparation example 4 obtain the UV, visible light near infrared absorption spectrogram of SWCNT dispersion liquid 1.

Fig. 4 in preparation example 5 obtain the UV, visible light near infrared absorption spectrogram of SWCNT dispersion liquid 2.

Fig. 5 in embodiment 2 obtain the UV, visible light near infrared absorption spectrogram of photocuring film 1.

Fig. 6 in embodiment 2 obtain photocuring film 1 in CHN/ water, flood the UV, visible light near infrared absorption spectrogram after 5 minutes.

Fig. 7 in comparative example 2 obtain the UV, visible light near infrared absorption spectrogram of photocuring film 2.

Fig. 8 in comparative example 2 obtain photocuring film 2 in CHN/ water, flood the UV, visible light near infrared absorption spectrogram after 5 minutes.

Embodiment

Below illustrate in greater detail the present invention.

Carbon material dispersion membrane of the present invention formation composition comprises the polymkeric substance containing triazine ring, linking agent and the carbon material containing the repeat unit structure represented by following formula (1).

[changing 4]

In above-mentioned formula, R and R ' represents hydrogen atom, alkyl, alkoxyl group, aryl or aralkyl independently of each other.

In the present invention, the carbon number as alkyl is not particularly limited, and is preferably 1 ~ 20, as improved the thermotolerance of polymkeric substance further, and more preferably carbon number 1 ~ 10, further preferably 1 ~ 3.In addition, its structure can be any one in chain, branched, ring-type.

As the concrete example of alkyl, methyl can be enumerated, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-normal-butyl, 2-methyl-normal-butyl, 3-methyl-normal-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-Dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl base, 2-ethyl-cyclopropyl base, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-normal-butyl, 1,2-dimethyl-normal-butyl, 1,3-dimethyl-normal-butyl, 2,2-dimethyl-normal-butyl, 2,3-dimethyl-normal-butyl, 3,3-dimethyl-normal-butyl, 1-ethyl-normal-butyl, 2-ethyl-normal-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-Ethyl-2-Methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-sec.-propyl-cyclopropyl, 2-sec.-propyl-cyclopropyl, 1,2,2-trimethylammonium-cyclopropyl, 1,2,3-trimethylammonium-cyclopropyl, 2,2,3-trimethylammonium-cyclopropyl, 1-Ethyl-2-Methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-Ethyl-2-Methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl etc.

Carbon number as above-mentioned alkoxyl group is not particularly limited, and is preferably 1 ~ 20, as improved the thermotolerance of polymkeric substance further, and more preferably carbon number 1 ~ 10, further preferably 1 ~ 3.In addition, the structure of its moieties can be any one in chain, branched, ring-type.

As the concrete example of alkoxyl group, methoxyl group can be enumerated, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1, 1-dimethyl-positive propoxy, 1, 2-dimethyl-positive propoxy, 2, 2-dimethyl-positive propoxy, 1-ethyl-positive propoxy, positive hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1, 1-dimethyl-n-butoxy, 1, 2-dimethyl-n-butoxy, 1, 3-dimethyl-n-butoxy, 2, 2-dimethyl-n-butoxy, 2, 3-dimethyl-n-butoxy, 3, 3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1, 1, 2-trimethyl-n-propoxy, 1, 2, 2-trimethyl-n-propoxy, 1-ethyl-1-methyl-positive propoxy, 1-Ethyl-2-Methyl-positive propoxy etc.

Carbon number as above-mentioned aryl is not particularly limited, and is preferably 6 ~ 40, as improved the thermotolerance of polymkeric substance further, and more preferably carbon number 6 ~ 16, further preferably 6 ~ 13.

As the concrete example of aryl, can enumerate phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, to fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, to cyano-phenyl, Alpha-Naphthyl, betanaphthyl, adjacent phenylbenzene, a phenylbenzene, to phenylbenzene, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl etc.

Carbon number as aralkyl is not particularly limited, and be preferably carbon number 7 ~ 20, its moieties can be any one in straight chain, side chain, ring-type.

As its concrete example, can enumerate benzyl, p-methylphenyl methyl, a methylphenylmethyl, adjacent Ethylphenylmethyl, an Ethylphenylmethyl, to Ethylphenylmethyl, 2-propylbenzene ylmethyl, 4-isopropyl benzene ylmethyl, 4-isobutyl-benzene ylmethyl, Alpha-Naphthyl methyl etc.

Above-mentioned Ar represents at least a kind in the group selecting free style (2) ~ (13) to represent.

[changing 5]

Above-mentioned R ¹~ R ⁹²represent the alkoxyl group of the alkyl of the had branched structure of hydrogen atom, halogen atom, carboxyl, sulfo group, carbon number 1 ~ 10 or the had branched structure of carbon number 1 ~ 10 independently of each other; W ¹and W ²represent singly-bound, CR independently of each other ⁹⁵r ⁹⁶(R ⁹⁵and R ⁹⁶represent the alkyl (wherein, they also can form ring together) of the had branched structure of hydrogen atom or carbon number 1 ~ 10 independently of each other), C=O, O, S, SO, SO ₂, or NR ⁹⁷(R ⁹⁷represent the alkyl of the had branched structure of hydrogen atom or carbon number 1 ~ 10); R ⁹³and R ⁹⁴represent the alkyl of the had branched structure of hydrogen atom or carbon number 1 ~ 10.

As halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be enumerated.

Be explained, as alkyl, alkoxyl group, group similar to the above can be enumerated.

In addition, X ¹and X ²the alkylidene group representing the had branched structure of singly-bound, carbon number 1 ~ 10 independently of each other or the group represented by formula (14).

[changing 6]

Above-mentioned R ⁹⁸~ R ¹⁰¹represent the alkoxyl group of the alkyl of the had branched structure of hydrogen atom, halogen atom, carboxyl, sulfo group, carbon number 1 ~ 10 or the had branched structure of carbon number 1 ~ 10 independently of each other; Y ¹and Y ²represent the alkylidene group of the had branched structure of singly-bound or carbon number 1 ~ 10 independently of each other.As these halogen atoms, alkyl, alkoxyl group, group similar to the above can be enumerated.

As the alkylidene group of the had branched structure of carbon number 1 ~ 10, methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene etc. can be enumerated.

Especially, as Ar, at least a kind that is preferably represented by formula (2), (5) ~ (13), at least a kind that is more preferably represented by formula (2), (5), (7), (8), (11) ~ (13).As the concrete example of the aryl represented by above-mentioned formula (2) ~ (13), the aryl represented by following formula can be enumerated, but be not limited to these aryl.

[changing 7]

Wherein, consider from the polymkeric substance obtaining more high refractive index, the aryl more preferably represented by following formula.

[changing 8]

Especially, as improved the solvability in the solvent that the securities such as resist solvent are high further, preferably containing the repeat unit structure represented by formula (15).

[changing 9]

(in formula, R, R ' and R ¹~ R ⁴represent implication same as described above.)

From the viewpoint, as particularly preferred repeat unit structure, the repeat unit structure represented by following formula (16) can be enumerated, with the high branched-chain polymer (hyperbranched polymer) represented by following formula (17) for best.

[changing 10]

(in formula, R and R ' represents implication same as described above.)

[changing 11]

In the present invention, the weight-average molecular weight for polymkeric substance is not particularly limited, and is preferably 500 ~ 500,000, more preferably 500 ~ 100,000, reducing shrinking percentage from the viewpoint of improving thermotolerance further simultaneously, being preferably 2, more than 000, from the viewpoint of improving solvability further, reduce institute and obtain the viscosity of solution, preferably 50, less than 000, be more preferably 30, less than 000, further preferably 10, less than 000.

Be explained, the weight-average molecular weight in the present invention is measured by gel permeation chromatography (hereinafter referred to as GPC) analysis, then the molecular-weight average converting according to polystyrene standard and obtain.

Polymkeric substance containing triazine ring of the present invention can adopt method disclosed in above-mentioned patent documentation 3 to prepare.

Such as, as shown in following flow process 1, the high branched-chain polymer (hyperbranched polymer) with repeat unit structure (17 ') can carry out reacting obtaining by making cyanuric halogen (18) and mphenylenediamine compound (19) in suitable organic solvent.

[changing 12]

(in formula, X represents halogen atom independently of each other; R represents implication same as described above.)

As shown in following flow process 2, the compound (20) that the high branched-chain polymer (hyperbranched polymer) with repeat unit structure (17 ') also can react with cyanuric halogen (18) and the mphenylenediamine compound (19) by equivalent and obtain in suitable organic solvent synthesizes.

[changing 13]

In the method for flow process 1 and 2, as the input amount of each raw material, as long as it can be just arbitrary for obtaining purpose polymers, relative to cyanuric halogen (18) 1 equivalent, diamino compounds (19) is preferably 0.01 ~ 10 equivalent.

Especially, when the method for flow process 1, relative to cyanuric halogen (18) 2 equivalent, preferably avoid the diamino compounds (19) of use 3 equivalent.As long as the equivalents of functional group is staggered, just can prevent from generating gel compound.

In order to obtain various molecular weight, the high branched-chain polymer (hyperbranched polymer) with multiple triazine ring end, relative to cyanuric halogen (18) 2 equivalent, preferably use diamino compounds (19) by the amount lower than 3 equivalents.

On the other hand, in order to obtain various molecular weight, the high branched-chain polymer (hyperbranched polymer) with multiple amine end, relative to diamino compounds (19) 3 equivalent, preferably use cyanuric halogen (18) by the amount lower than 2 equivalents.

Such as, when making film, from the viewpoint of having the excellent transparency and photostabilization, preferably there is the high branched-chain polymer (hyperbranched polymer) of multiple triazine ring end.

As above-mentioned organic solvent, normally used all kinds of SOLVENTS in this reaction can be used in, can enumerate such as, tetrahydrofuran (THF), two alkane, methyl-sulphoxide; N; dinethylformamide, METHYLPYRROLIDONE, tetramethyl-urea, hexamethylphosphoramide, N; N-N,N-DIMETHYLACETAMIDE, N-methyl-2-piperidone, N; N-dimethyl ethylene urea, N; N; N '; N '-tetramethyl-Malonamide, N-methyl caprolactam, N-acetyl-pyrrolidine, N; N-diethyl acetamide, N-ethyl-2-pyrrolidone, N; N-dimethylpropionamide, N; N-dimethyl isobutyl acid amides, N-METHYLFORMAMIDE, N, acid amides series solvent and their mixed solvents such as N '-dimethyl propylidene urea.

Wherein, preferred DMF, methyl-sulphoxide, METHYLPYRROLIDONE, N,N-dimethylacetamide and their mixed solvent, particularly preferably N,N-dimethylacetamide, METHYLPYRROLIDONE.

In the reaction in the 2nd stage of flow process 1 and flow process 2, set as long as temperature of reaction is suitable in from the fusing point of solvent for use to the scope of boiling point, especially, preferably about 0 ~ 150 DEG C, be more preferably 60 ~ 100 DEG C.

Especially, in the reaction of flow process 1, raising side chain degree linear from the viewpoint of suppression, temperature of reaction is preferably 60 ~ 150 DEG C, is more preferably 80 ~ 150 DEG C, more preferably 80 ~ 120 DEG C.

In the reaction in the 1st stage of flow process 2, as long as temperature of reaction is suitable for setting in from the fusing point of solvent for use to the scope of solvent boiling point, especially, be preferably about-50 ~ 50 DEG C, be more preferably about-20 ~ 50 DEG C, more preferably about-10 ~ 50 DEG C, be further preferably-10 ~ 10 DEG C.

Particularly in the method for flow process 2, preferably adopt 2 stage procedures, be wherein included in the 1st operation of to carry out at-50 ~ 50 DEG C reacting and after this operation, at 60 ~ 150 DEG C, carry out the 2nd operation of reacting.

In above-mentioned each reaction, the cooperation order of each composition is arbitrary, in the reaction of flow process 1, optimum method is, solution containing cyanuric halogen (18) or diamino compounds (19) and organic solvent is heated to 60 ~ 150 DEG C, preferably 80 ~ 150 DEG C, at such a temperature, in this solution, diamino compounds (19) or cyanuric halogen (18) is added.

In this situation, be dissolved in advance composition in solvent and the follow-up composition added be no matter any can, in the heated solution of diamino compounds (19), preferably add the method for cyanuric halogen (18).

In addition, in the reaction of flow process 2, be dissolved in advance composition in solvent and the follow-up composition added be no matter any can, in the cooling solution of cyanuric halogen (18), preferably add the method for diamino compounds (19).

The follow-up composition added can add by the form of pure substance, also can add by the above-mentioned solution be dissolved in like that in organic solvent, if consider the easiness of operation and be easy to control to reaction, the method for preferred the latter.

In addition, interpolation can be adopt dropping etc. slowly to add, and also can be full dose added once.

In flow process 1, after two kinds of compound of heating condition, even if when making it react by one-phase (not being periodically improve temperature), the high branched-chain polymer (hyperbranched polymer) containing triazine ring as target product also can be obtained under the condition that gelation does not occur.

In addition, in the reaction in the 2nd stage of above-mentioned flow process 1 and flow process 2, when being polymerized or after polymerisation, normally used various alkali can also be added.

As the concrete example of this alkali, salt of wormwood, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethylate, sodium acetate, Quilonum Retard, lithium hydroxide, Lithium Oxide 98min, potassium acetate, magnesium oxide, calcium oxide, hydrated barta, tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, Trimethylamine 99, triethylamine, Diisopropylamine, diisopropylethylamine, N-methyl piperidine, 2 can be enumerated, 2,6,6-tetramethyl--N-methyl piperidine, pyridine, DMAP, N-methylmorpholine etc.

Relative to cyanuric halogen (18) 1 equivalent, the addition of alkali is preferably 1 ~ 100 equivalent, more preferably 1 ~ 10 equivalent.Be explained, these alkali also can be made the aqueous solution to use.

In the method for any one flow process, after the completion of reaction, resultant can adopt reprecipitation method etc. easily to refine.

Be explained, in the present invention, also a part of halogen atom alkyl of at least 1 end triazine ring, aralkyl, aryl, alkylamino, alkylamino, aryl alkyl amino, arylamino, alkoxyl group, aralkoxy, aryloxy, ester group etc. containing alkoxysilyl can be carried out end-blocking.

Wherein, preferred alkyl amino, the alkylamino containing alkoxysilyl, aryl alkyl amino, arylamino, more preferably alkylamino, arylamino, further preferred aryl groups is amino.

As abovementioned alkyl, alkoxyl group, group similar to the above can be enumerated.

As the concrete example of ester group, methoxycarbonyl, ethoxy carbonyl etc. can be enumerated.

As the concrete example of aralkyl, can enumerate benzyl, p-methylphenyl methyl, a methylphenylmethyl, adjacent Ethylphenylmethyl, an Ethylphenylmethyl, to Ethylphenylmethyl, 2-propylbenzene ylmethyl, 4-isopropyl benzene ylmethyl, 4-isobutyl-benzene ylmethyl, Alpha-Naphthyl methyl etc.

As the concrete example of alkylamino, methylamino-can be enumerated, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, i-butylamino, Zhong Ding is amino, tertiary fourth is amino, pentylamine base, 1-methyl-n-butyl amine base, 2-methyl-n-butyl amine base, 3-methyl-n-butyl amine base, 1, 1-dimethyl-n-propylamine base, 1, 2-dimethyl-n-propylamine base, 2, 2-dimethyl-n-propylamine base, 1-ethyl-n-propylamine base, just oneself is amino, 1-methyl-pentylamine base, 2-methyl-pentylamine base, 3-methyl-pentylamine base, 4-methyl-pentylamine base, 1, 1-dimethyl-n-butyl amine base, 1, 2-dimethyl-n-butyl amine base, 1, 3-dimethyl-n-butyl amine base, 2, 2-dimethyl-n-butyl amine base, 2, 3-dimethyl-n-butyl amine base, 3, 3-dimethyl-n-butyl amine base, 1-ethyl-n-butyl amine base, 2-ethyl-n-butyl amine base, 1, 1, 2-trimethylammonium-n-propylamine base, 1, 2, 2-trimethylammonium-n-propylamine base, 1-ethyl-1-methyl-n-propylamine base, 1-Ethyl-2-Methyl-n-propylamine base etc.

As the concrete example of aryl alkyl amino, can enumerate benzyl amino, methoxycarbonyl-phenyl methylamino-, carboethoxyphenyl methylamino-, p-methylphenyl methylamino-, an aminomethyl phenyl methylamino-, adjacent ethylphenyl methylamino-, an ethylphenyl methylamino-, to ethylphenyl methylamino-, 2-propyl group phenyl methylamino-, 4-isopropyl phenyl methylamino-, 4-isobutyl phenenyl methylamino-, napthylmethylamino, methoxycarbonyl napthylmethylamino, ethoxy carbonyl napthylmethylamino etc.

As the concrete example of arylamino, phenylamino, methoxycarbonyl phenylamino, ethoxy carbonyl phenylamino, naphthylamino, methoxycarbonyl naphthylamino, ethoxy carbonyl naphthylamino can be enumerated, anthracene is amino, pyrene is amino, diphenylamino, three phenylaminos, fluorenes are amino.

As the alkylamino containing alkoxysilyl, it can be the alkylamino containing monoalkoxy silyl, alkylamino containing dialkoxy silyl, containing any one in the alkylamino of trialkoxysilyl, as its concrete example, 3-trimethoxysilyl third can be enumerated amino, 3-triethoxysilyl third is amino, 3-dimethylethyloxy silyl third is amino, 3-methyl diethoxy silyl third is amino, N-(2-aminoethyl)-3-dimethylmethoxysilylgroups groups third is amino, N-(2-aminoethyl)-3-methyl dimethoxy oxygen base silyl third is amino, N-(2-aminoethyl)-3-trimethoxysilyl third amino etc.

As the concrete example of aryloxy, phenoxy group, naphthyloxy, anthracene oxygen base, pyrene oxygen base, two phenoxy groups, triple phenoxyl, fluorenes oxygen base etc. can be enumerated.

As the concrete example of aralkoxy, can enumerate benzyloxy, p-methylphenyl methoxyl group, a methyl phenyl methoxy, adjacent ethylphenyl methoxyl group, an ethylphenyl methoxyl group, to ethylphenyl methoxyl group, 2-propylbenzene ylmethoxy, 4-isopropyl benzene ylmethoxy, 4-isobutyl-benzene ylmethoxy, Alpha-Naphthyl methoxyl group etc.

These groups can by easily introducing with the substituent compound corresponding with the halogen atom on triazine ring can be provided to carry out replacement, such as, as shown in following formula flow process 3, making it react by adding anils, the high branched-chain polymer (21) at least on 1 end with phenylamino can be obtained.

[changing 14]

(in formula, X and R represents implication same as described above.)

Now, reinforced while carrying out organic monoamine, that is, under the existence of organic monoamine, by making cyanuric halogen compound and diamino aryl compound react, the rigidity that can obtain hyperbranched polymer becomes mitigation, flexible hyperbranched polymer that side chain degree is low.

Adopt the hyperbranched polymer that obtains of the method, its solvability (condensing suppressed) in a solvent, all excellent with the bridging property of linking agent.

At this, as organic monoamine, any one in alkyl monoamine, aralkyl monoamine, aryl monoamine also can be used.

As alkyl monoamine, methylamine can be enumerated, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, n-amylamine, 1-methyl-n-Butyl Amine 99, 2-methyl-n-Butyl Amine 99, 3-methyl-n-Butyl Amine 99, 1, 1-dimethyl-Tri N-Propyl Amine, 1, 2-dimethyl-Tri N-Propyl Amine, 2, 2-dimethyl-Tri N-Propyl Amine, 1-ethyl-Tri N-Propyl Amine, normal hexyl Amine, 1-methyl-n-amylamine, 2-methyl-n-amylamine, 3-methyl-n-amylamine, 4-methyl-n-amylamine, 1, 1-dimethyl-nbutylamine, 1, 2-dimethyl-nbutylamine, 1, 3-dimethyl-nbutylamine, 2, 2-dimethyl-nbutylamine, 2, 3-dimethyl-nbutylamine, 3, 3-dimethyl-nbutylamine, 1-ethyl-n-Butyl Amine 99, 2-ethyl-n-Butyl Amine 99, 1, 1, 2-trimethylammonium-Tri N-Propyl Amine, 1, 2, 2-trimethylammonium-Tri N-Propyl Amine, 1-ethyl-1-methyl-Tri N-Propyl Amine, 1-Ethyl-2-Methyl-Tri N-Propyl Amine, 2 ethyl hexylamine etc.

As the concrete example of aralkyl monoamine, benzylamine can be enumerated, to methoxycarbonyl benzylamine, to carboethoxyphenyl benzyl, to methylbenzylamine, a methylbenzylamine, O-methoxy benzylamine etc.

As the concrete example of aryl monoamine, can enumerate aniline, to methoxycarbonyl aniline, to ethoxy carbonyl aniline, P-nethoxyaniline, naphthalidine, 2-naphthylamines, anthranylamine, the amino pyrene of 1-, 4-pentanoic, adjacent phenylaniline, 4-amino-to hexichol, 2-aminofluorene etc.

In this situation, relative to cyanuric halogen compound, the usage quantity of organic monoamine, is preferably 0.05 ~ 500 equivalent, is more preferably 0.05 ~ 120 equivalent, more preferably 0.05 ~ 50 equivalent.

About the temperature of reaction in this situation, raising side chain degree linear from the viewpoint of suppression, temperature of reaction is preferably 60 ~ 150 DEG C, is more preferably 80 ~ 150 DEG C, more preferably 80 ~ 120 DEG C.

But the mixing of organic monoamine, cyanuric halogen compound, these 3 kinds of compositions of diamino aryl compound, also can carry out at a lower temperature, as the temperature of this situation, be preferably about-50 ~ 50 DEG C, be more preferably about-20 ~ 50 DEG C, more preferably-20 ~ 10 DEG C.After low temperature is reinforced, preferably the disposable temperature (heating up by one-phase) making it be polymerized that is warming up to is reacted.

In addition, cyanuric halogen compound also can carry out under low temperature with mixing of these 2 kinds of compositions of diamino aryl compound, as this situation temperature, be preferably about-50 ~ 50 DEG C, be more preferably about-20 ~ 50 DEG C, more preferably-20 ~ 10 DEG C.After low temperature is reinforced, preferably add organic monoamine, the disposable temperature (heating up by one-phase) making it be polymerized that is warming up to is reacted.

In addition, under the existence of this organic monoamine, make the reaction of cyanuric halogen compound and diamino aryl compound, also can use organic solvent similar to the above to carry out.

As the linking agent used in carbon material dispersion membrane formation composition of the present invention, can carry out with the above-mentioned polymkeric substance containing triazine ring the substituent compound that reacts as long as have, just be not particularly limited.

As this compounds, can enumerate and there is methylol, methoxymethyies etc. are cross-linked to form substituent melamine based compound, substituted urea based compound, there is epoxy group(ing) or oxetanyl etc. and be cross-linked to form substituent compound, there is the compound of isocyanate group, there is the compound of end-blocking isocyanic ester, there is the compound of acid anhydrides, there is the compound of (methyl) acrylic, phenolic resin compound etc., from the viewpoint of thermotolerance and storage stability, preferably there is epoxy group(ing), isocyanate group, blocked isocyanate ester group, the compound of (methyl) acrylic, particularly preferably there is the compound of isocyanate group, even and if do not use initiator can form multi-functional epoxy compound and/or multifunctional (methyl) acrylic compounds of photo curable composition yet.

Be explained, when the end-o f-pipe-control for polymkeric substance, as long as these compounds have at least 1 be cross-linked to form substituting group, when for crosslinking Treatment between polymkeric substance, these compounds must have at least 2 and be cross-linked to form substituting group.

As multi-functional epoxy compound, as long as have more than 2 epoxy group(ing) in a part, be just not particularly limited.

As its concrete example, three (2 can be enumerated, 3-epoxypropyl) isocyanuric acid ester, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4-(epoxy ethyl) hexanaphthene, T 55, glycol ether diglycidylether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 1, 3-tri-is [to (2, 3-glycidoxy) phenyl] propane, 1, 2-cyclohexane dicarboxylic acid 2-glycidyl ester, 4, 4 '-methylene-bis (N, N-diglycidylaniline), 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexane carboxylate, trimethylolethane trimethacrylate glycidyl ether, bisphenol-A-diglycidylether, tetramethylolmethane polyglycidyl ether etc.

In addition, as commercially available product, also can use: belong to the epoxy resin with at least 2 epoxy group(ing): YH-434, YH434L (Dongdu changes into (strain) system); Belong to the epoxy resin with epoxy cyclohexane structure: EpoleadGT-401, GT-403, GT-301, GT-302, Celloxide2021,3000 (Daicel chemical industry (strain) systems); Belong to bisphenol A type epoxy resin: Epikote (existing, jER) 1001,1002,1003,1004,1007,1009,1010,828 (being made by japan epoxy resin (strain) above); Belong to bisphenol f type epoxy resin: Epikote (existing, jER) 807 (japan epoxy resin (strain) systems); Belong to novolac type epoxy resins: Epikote (existing, jER) 152,154 (being made by japan epoxy resin (strain) above), EPPN201,202 (being made by Japanese chemical drug (strain) above); Belong to cresol novolak type epoxy resin: EOCN-102,103S, 104S, 1020,1025,1027 (being made by Japanese chemical drug (strain) above), Epikote (existing, jER) 180S75 (japan epoxy resin (strain) system); Belong to alicyclic epoxy resin: DenacolEX-252 (NagaseChemtex (strain) system), CY175, CY177, CY179 (above by CIBA-GEIGYA.G system); AralditeCY-182, CY-192, CY-184 (above by CIBA-GEIGYA.G system); Epiclon200,400 (being made by DIC (strain) above); Epikote (existing, jER) 871,872 (being made by japan epoxy resin (strain) above); ED-5661, ED-5662 (being made by CelaneseCoating (strain) above); Belong to aliphatics polyglycidyl ether: DenacolEX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (NagaseChemtex (strain) system) etc.

As multifunctional (methyl) acrylic compounds, as long as have more than 2 (methyl) acrylics in a part, be just not particularly limited.

As its concrete example, ethylene glycol diacrylate can be enumerated, Ethylene glycol dimethacrylate, diacrylate macrogol ester, PEGDMA-400, ethoxylated bisphenol a diacrylate, Ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylation tetramethylol methane tetraacrylate, ethoxylation pentaerythritol tetramethylacrylate, ethoxylated dipentaerythritol six acrylate, Polyglycerine monocycle oxidative ethane polyacrylic ester, Polyglycerine polyoxyethylene glycol polyacrylic ester, six vinylformic acid dipentaerythritol ester, hexamethyl vinylformic acid dipentaerythritol ester, diacrylic acid pentyl diol ester, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, trimethacrylate acid pentaerythritol ester, Viscoat 295, trimethylolpropane trimethacrylate, Tricyclodecane Dimethanol diacrylate, Tricyclodecane Dimethanol dimethacrylate, diacrylate 1,6-hexylene glycol ester, dimethacrylate 1,6-hexylene glycol ester etc.

In addition, multifunctional (methyl) acrylic compounds can be buied as commercially available product, as its concrete example, NKESTERA-200 can be enumerated, A-400, A-600, A-1000, A-9300 (isocyanuric acid three (2-acryloyl-oxyethyl) ester), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E (being made by Xin Zhong village chemical industry (strain) above), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (being made by Japanese chemical drug (strain) above), M-210, M-350 (synthesizing (strain) by East Asia above to make), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (being made by Japanese chemical drug (strain) above), NKESTERA-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (being made by Xin Zhong village chemical industry (strain) above), NKOligoU-15HA (Xin Zhong village chemical industry (strain) system), NKPolymerVanaresinGH-1203 (Xin Zhong village chemical industry (strain) system) etc.

As anhydride compound, as long as the carboxylic acid anhydride of the carboxylic acid dehydrating condensation by 2 molecules, just be not particularly limited, as its concrete example, phthalate anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride, methyl tetrahydrochysene phthalate anhydride, methyl hexahydrophthalic acid anhydride, 4-norbornylene-1 can be enumerated, 2-dicarboxylic anhydride, methyl 4-norbornylene-1,2-dicarboxylic anhydride, maleic anhydride, succinyl oxide, octyl group succinyl oxide, dodecenyl succinic anhydride etc. have the compound of 1 anhydride group in molecule, 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, pyromellitic dianhydride, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dianhydride, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic dianhydride, 5-(2, 5-dioxidotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-biphenyltetracaboxylic dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride etc. has the compound etc. of 2 anhydride group in molecule.

As the compound with isocyanate group, as long as have more than 2 isocyanate group in a part, and crosslinking reaction between resin will be caused once isocyanate group under the high temperature being exposed to thermofixation, just be not particularly limited, can enumerate such as, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), the polyisocyanates of trimethyl hexamethylene diisocyanate, or their dipolymer, trimer, and they and glycols, three alcohols, Diamines, or the reactant etc. of three amines.

In addition, isocyanate compound can be buied as commercially available product, as its concrete example, can enumerate MillioateMT, MT-F, NM, NM100, MP-100, MR-200, MR-400, MTL, Coronate1130, 1050, 1057, 1108, 1120, 1316, MX, 1021, 1025, T-80, T65, T100, L, L-55E, L-45E, 2067, 2030, 2031, 2037, 2050, 2071, 2232, 2233, 342, 2014, 2041, 2222, HX, HXR, HXLV, HK, 2715, 2770, HX-T, HL, AP-M, BI-301, 2507, 3015E, 3030E, 3060, Nippolan3109, 2304, 3114, 3124, 3230, 3004, Aquanate105, 110, 140, 210, Woodlock, Woodcure220, 300 (above by Nippon Polyurethane Industry (Ltd.)), BurnockD-750, D-800, DN-902S, DN-950, DN-955, DN-980, DN-981, DN-990, DN-992 (being made by DIC (strain) above) Duranate (registered trademark) 24A-100, 22A-75P, 21S-75E, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, TSA-100, TSS-100, TSE-100, P301-75E, E402-80B, E405-70B, AE700-100, D101, D201, A201H (being made by Asahi Chemical Industry Chemicals (strain) above) etc.

And then, when use there is isocyanate group compound as linking agent, also can be used together polyol compound, as the polyurethane cross-linking agent on end with isocyanate group.

As polyol compound, can enumerate such as, low molecular polyhydroxy reactant or the thermoplastic urethane resins etc. such as acrylic polyol resin, polyester polyol resin, polyether polyol resin, polytetramethylene ether diol (PTMG), polycarbonate diol, polycaprolactone glycol, they can be used alone a kind, also two or more can be combinationally used.In addition, in order to control curing reaction, also the catalyzer such as normally used organo-tin compound can be added in carbamate resins.

Polyol compound also can be bought as commercially available product, as its concrete example, can enumerate Nippolan121E, 125E, 179P, 131,800,1100,4002,4040,4009,4010,3027,164,4073,136,152,1004,141,4042,163,5018,5035,981,980R, 982R, 963,964, PC-61 (above by Nippon Polyurethane Industry (Ltd.)), AcrydicA-801-P, A-817, A-837, A-848-RN, A-814, 57-773, A-829, 55-129, 49-394-IM, A-875-55, A-870, A-871, A-859-B, 52-666-BA, 52-668-BA, WZU-591, WXU-880, BL-616, CL-100, CL-408, Burnock11-408, D-210-80, D-161, J-517, D-128-65BA, D-144-65BA, D-145-55BA, PolyliteRX-4800, OD-X-2251, OD-X-2523, OD-X-2547, OD-X-2555, OD-X-2420, OD-X-2692, OD-X-2586, OD-X-102, OD-X-668, OD-X-2420, OD-X-2068, OD-X-2108, OD-X-688, OD-X-2155, OD-X-640, OD-X-2722, (being made by DIC (strain) above), AdekaPolyetherP is serial, BPX is serial, G is serial, T is serial, EDP is serial, SC, SP are serial, AM is serial, BM is serial, CM is serial, PR is serial, GR is serial, FC-450, AdekaNewaceNS-2400, YT-101, F7-67, #50, F-1212-29, YG-108, V-14-90, Y-65-55 (above by (strain) ADEKA system), PTMG650,850,1000,1300,1500,1800,2000,3000 (above by Mitsubishi Chemical's (strain) make), PraccelCD205PL, CD210,220,220PL (above by Daicel chemical industry (strain) make) etc.

About the compound containing end-blocking isocyanic ester, as long as there are more than 2 in its a part by isocyanate group (-NCO) by the end-blocking isocyanate group of suitable protecting group end-blocking, once under the high temperature being exposed on thermofixation, protecting group (end) will be left away by pyrolysis, and the isocyanate group generated can cause the crosslinking reaction between resin, such compound is just not particularly limited, can enumerate such as, there are more than 2 groups represented by following formula in a part (be explained, these groups can be identical, also can be different separately) compound.

[changing 15]

(in formula, R _brepresent the organic group in end-blocking portion.)

This compound by such as, can make suitable end-capping reagent and the above-mentioned compound in a part with more than 2 isocyanate group carry out reaction and obtains.

As end-capping reagent, can enumerate such as, the alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, 2-oxyethyl group hexanol, 2-N, N-dimethylaminoethanol, cellosolvo, hexalin; Phenol, o-NP, para-chlorophenol, neighbour, or the phenol such as p-cresol; The lactams such as ε-caprolactam; The oximes such as acetoxime, methyl ethyl ketone oxime, methyl isobutyl ketoxime, cyclohexanone-oxime, acetophenone oxime, diphenylketoxime; The pyrazoleses such as pyrazoles, 3，5-dimethylpyrazole, 3-methylpyrazole; The thio-alcohol such as lauryl mercaptan, benzenethiol etc.

Compound containing end-blocking isocyanic ester also can be bought as commercially available product, as its concrete example, B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (being made by Mitsui Chemicals urethane (strain) above) can be enumerated; Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (being made by Asahi Chemical Industry Chemicals (strain) above); KarenzMOI-BM (registered trademark) (being made by Showa electrician (strain) above) etc.

As aminoplastics (aminoplast) compound, as long as have more than 2 methoxymethylene in a part, just be not particularly limited, can enumerate such as, the Cymel series such as hexamethoxy methyl cyanuramide CYMEL (registered trademark) 303, four butoxymethyl glycoluril 1170, tetramethoxymethyl benzo guanamine 1123 (being made by Japanese CytecIndustries (strain) above); Belong to Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM of methylated melamines resin; Belong to the melamine based compounds such as Nikalac series such as MX-270, MX-280MX-290 (above by (strain) three and Chemical system) of methylated urea resins.

As oxetane compound, as long as more than 2 oxetanyl bases in a part, just be not particularly limited, can enumerate such as, OXT-221, OX-SQ-H, OX-SC (synthesizing (strain) by East Asia above to make) etc. containing oxetanyl.

Phenolic resin compound is such compounds, has more than 2 hydroxy methylenes in its a part, and under the high temperature being exposed to thermofixation just by the dehydration condensation between polymkeric substance of the present invention to carry out crosslinking reaction.

As phenolic resin compound; can enumerate such as; 2; 6-dihydroxymethyl-4-methylphenol, 2; 4-dihydroxymethyl-6-methylphenol, two (2-hydroxyl-3-methylol-5-aminomethyl phenyl) methane, two (4-hydroxyl-3-methylol-5-aminomethyl phenyl) methane, 2; two (the 4-hydroxyl-3 of 2-; 5-dihydroxymethyl phenyl) propane, two (3-formyl radical-4-hydroxyphenyl) methane, two (4-hydroxyl-2; 5-3,5-dimethylphenyl) formyl radical methane, α; α-bis-(4-hydroxyl-2,5-3,5-dimethylphenyl)-4-formyl radical toluene etc.

Phenolic resin compound also can be bought as commercially available product, as its concrete example, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (being made by the organic material industry (strain) of the rising sun above) etc. can be enumerated.

Wherein, reduce from the viewpoint of the specific refractory power that can suppress owing to coordinating linking agent to cause, curing reaction is carried out rapidly simultaneously, preferably multifunctional (methyl) acrylic compounds, wherein, from the viewpoint of excellent with the intermiscibility of the polymkeric substance containing triazine ring, more preferably there is multifunctional (methyl) acrylic compounds of following isocyanuric acid skeleton.

As multifunctional (methyl) acrylic compounds with this skeleton, can enumerate such as, NKESTERA-9300, A-9300-1CL (by Xin Zhong village chemical industry (strain) system).

[changing 16]

(in formula, R ¹⁰²~ R ¹⁰⁴represent monovalent organic group end with at least 1 (methyl) acrylic independently of each other.)

In addition, from the viewpoint of improve further curing speed, simultaneously improve obtain solvent resistance and acid resistance, the alkali resistance of cured film, preferably when 25 DEG C will be liquid and its viscosity be below 5000mPas, preferably 1 ~ 3000mPas, more preferably 1 ~ 1000mPas, further preferably multifunctional (methyl) acrylic compounds (hereinafter referred to as low viscosity linking agent) of 1 ~ 500mPas individually or two or more combinationally use, or to combinationally use with multifunctional (methyl) acrylic compounds with above-mentioned isocyanuric acid skeleton.

This low viscosity linking agent also can be bought as commercially available product, can enumerate such as, in above-mentioned multifunctional (methyl) acrylic compounds, NKESTERA-GLY-3E (85mPas, 25 DEG C), A-GLY-9E (95mPas, 25 DEG C), A-GLY-20E (200mPas, 25 DEG C), A-TMPT-3EO (60mPas, 25 DEG C), A-TMPT-9EO, ATM-4E (150mPas, 25 DEG C), ATM-35E (350mPas, 25 DEG C) (being made by Xin Zhong village chemical industry (strain) above) etc., the linking agent that chain length between (methyl) acrylic is long.

And then, consider that improve institute obtains the alkali resistance of cured film simultaneously, preferably by least one party in NKESTERA-GLY-20E (Xin Zhong village chemical industry (strain) system) and ATM-35E (Xin Zhong village chemical industry (strain) system), and multifunctional (methyl) acrylic compounds with above-mentioned isocyanuric acid skeleton combinationally use.

Above-mentioned linking agent may be used alone, or two or more kinds may be used in combination.Relative to polymkeric substance 100 mass parts containing triazine ring, the usage quantity of linking agent is preferably 1 ~ 100 mass parts, considers solvent resistance, its lower limit is preferably 2 mass parts, is more preferably 5 mass parts, and then, consider control specific refractory power, its upper limit is preferably 20 mass parts, is more preferably 15 mass parts.

In the purposes of decoration coating or ink, relative to polymkeric substance 100 mass parts containing triazine ring, the usage quantity of linking agent is preferably 1 ~ 1000 mass parts, consider solvent resistance, its lower limit is preferably 2 mass parts, is more preferably 5 mass parts, and then, consider the dispersiveness controlling carbon material, its upper limit is preferably 300 mass parts, is more preferably 100 mass parts.

In carbon material dispersion membrane formation composition of the present invention, also can coordinate the initiator corresponding with each linking agent.Be explained, as mentioned above, when using multi-functional epoxy compound and/or multifunctional (methyl) acrylic compounds as linking agent, even if do not use initiator, also can carry out photocuring and form cured film, in this situation, use initiator also harmless.

When using multi-functional epoxy compound as linking agent, light acid propellant or light alkali propellant can be used.

As light acid propellant, as long as be suitable for choice for use from known light acid propellant, can use such as, diazonium salt, sulfonium salt or iodine salt etc. salt derivative.

As its concrete example, phosphofluoric acid phenyldiazonium can be enumerated salt, hexafluoro-antimonic acid 4-p-methoxy-phenyl diazonium salt, phosphofluoric acid 4-aminomethyl phenyl diazonium the aryldiazonium such as salt salt, hexafluoro-antimonic acid phenylbenzene iodine salt, phosphofluoric acid two (4-aminomethyl phenyl) iodine salt, phosphofluoric acid two (4-tert-butyl-phenyl) iodine the Diaryl iodonium such as salt salt, hexafluoro-antimonic acid triphenyl sulfonium salt, phosphofluoric acid three (4-p-methoxy-phenyl) sulfonium salt, hexafluoro-antimonic acid phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium salt, phosphofluoric acid phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium salt, 4, 4 '-bis-(phenylbenzene sulfonic group) aralkyl sulfid-bis-hexafluoro antimonate, 4, 4 '-bis-(phenylbenzene sulfonic group) aralkyl sulfid-bis-hexafluorophosphate, 4, 4 '-bis-[two (beta-hydroxy oxyethyl group) phenylbenzimidazole sulfonic acid base] aralkyl sulfid-bis-hexafluoro antimonate, 4, 4 '-bis-[two (beta-hydroxy oxyethyl group) phenylbenzimidazole sulfonic acid base] aralkyl sulfid-bis--hexafluorophosphate, 4-[4 '-(benzoyl) phenyl] phenyl-two (4-fluorophenyl) hexafluoro-antimonic acid sulfonium salt, the triarylsulfonium salts etc. such as 4-[4 '-(benzoyl) phenyl] phenyl-two (4-fluorophenyl) phosphofluoric acid sulfonium salt.

These salt can use commercially available product, as its concrete example, San-AidSI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, SI-L147 (being made by three new chemical industry (strain) above) can be enumerated; UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above by UnionCarbide society system); CPI-100P, CPI-100A, CPI-200K, CPI-200S (being made by San-Apro (strain) above); AdekaOptomerSP-150, SP-151, SP-170, SP-171 (being made by rising sun electrochemical industry (strain) above); Irgacure261 (BASF AG's system); CI-2481, CI-2624, CI-2639, CI-2064 (being made by Japanese Cao Da (strain) above); CD-1010, CD-1011, CD-1012 (above by Sartomer society system); DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOINTOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (being made by Midori chemistry (strain) above); PCI-061T, PCI-062T, PCI-020T, PCI-022T (being made by Japanese chemical drug (strain) above); IBPF, IBCF (three and Chemical (strain) system) etc.

On the other hand, as light alkali propellant, as long as be suitable for choice for use from known smooth alkali propellant, can use such as, Co-amine complex system, oxime carboxylate system, carbamate system, quaternary ammonium salt system light alkali propellant etc.

As its concrete example, 2-nitrobenzyl cyclohexylcarbamate can be enumerated, triphenylcarbinol, O-formamyl oxyamide, O-formamyl oxime, [[(2, 6-dinitrobenzyl) oxygen base] carbonyl] hexahydroaniline, two [[(2-nitrobenzyl) oxygen base] carbonyl] hexane 1, 6-diamines, 4-(methyl thio benzoyl)-1-methyl isophthalic acid-morpholino ethane, (4-morpholino benzoyl)-1-benzyl-1-dimethylamino-propane, N-(2-nitrobenzyloxycarbonyl) tetramethyleneimine, six cobaltammines (III) three (trityl group borate), 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone, 2, 6-dimethyl-3, 5-diacetyl-4-(2 '-nitrophenyl)-1, 4-dihydropyridine, 2, 6-dimethyl-3, 5-diacetyl-4-(2 ', 4 '-dinitrophenyl)-1, 4-dihydropyridine etc.

In addition, as light alkali propellant, can commercially available product be used, as its concrete example, TPS-OH, NBC-101, ANC-101 (be goods name, Midori chemistry (strain) is made) etc. can be enumerated.

When using light acid propellant or light alkali propellant, relative to multi-functional epoxy compound 100 mass parts, preferably in the scope of 0.1 ~ 15 mass parts, more preferably use in the scope of 1 ~ 10 mass parts.

Be explained, also as required, relative to multi-functional epoxy compound 100 mass parts, epoxy curing agent can be coordinated by the amount of 1 ~ 100 mass parts.

On the other hand, when using multifunctional (methyl) acrylic compounds, optical free radical polymerization starter can be used.

As optical free radical polymerization starter; as long as suitable choice for use from known optical free radical polymerization starter; can enumerate such as, acetophenones, benzophenone, rice Chi Le Shi (Michler ' s) benzoylbenzoate, amyl group oxime (amyloxide) ester, oxime ester class, tetramethylthiuram monosulfide and thioxanthene ketone etc.

The optical free radical polymerization starter of particularly preferably photolysis type.For the optical free radical polymerization starter of photolysis type, be recorded in up-to-date UV curing technology (159 pages, publisher: high thin one great, sale room: (strain) technical intelligence association, distribution in 1991).

As commercially available optical free radical polymerization starter, can enumerate such as, BASF AG's trade(brand)name: Irgacure127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, Darocur1116, 1173, MBF, BASF AG's trade(brand)name: LucirinTPO, UCB. S.A.'s trade(brand)name: UbecrylP36, FratelliLamberti society trade(brand)name: EsacureKIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B etc.

When using optical free radical polymerization starter, relative to multifunctional (methyl) acrylic compound 100 mass parts, preferably using in the scope of 0.1 ~ 200 mass parts, more preferably using in the scope of 1 ~ 150 mass parts.

The carbon material that carbon material dispersion membrane formation composition of the present invention uses, in order to improve the electroconductibility of obtained cured film, sliding, opacifying property coordinate, and can be suitable for choice for use from known carbon material.As the concrete example of carbon material, CNT, carbon nanohorn, soccerballene, Graphene, carbon black, section's qin carbon black, graphite, carbon fiber etc. can be enumerated, preferred CNT or carbon black.In the present invention, they may be used alone, can also be 2 or more kinds in combination.

Carbon nanotube adopts arc discharge method, chemical Vapor deposition process (CVD), laser ablation method etc. to make, and the CNT used in the present invention adopts any method to obtain.In addition, CNT exist by 1 carbon film (graphene film) be rolled into cylindric individual layer CNT (being hereafter abbreviated as SWCNT), by 2 Graphene film rolling concentrically 2 layers of CNT (being hereafter abbreviated as DWCNT) of round shape and multi-disc graphene film be rolled into concentrically ringed multi-layer C NT (being hereafter abbreviated as MWCNT) etc., any one CNT can be used in the present invention.

Particularly, following commercially available product etc. can be used.

KHSWCNTED, EP, HP, (above by KHChemicals Inc.).

ASA-100F, AST-100F, ASP-100F, CMP310F, 320F, 330F, 340F, 1340F, CM95,100, PE-100 (above by HanwhaNanotech Inc.).

SWNT1,2, DWNT1,2, L.B-MWNTs10,10A, Aligned-MWNT, HBNTHerrin-bone, MWNTs (above by ShenzhenNanotech Inc.).

SWNTFH-A, FH-P, APJ, SO, MWNT (above by well-known city NanoCarbon society system).

Nanocyl7000 (Nanocyl Inc.).

BaytubeC150P, 70P (above by Bayer Inc.).

AMC (UBE Inc.).

VGCF-H (Showa electrician (strain) system).

MWNT-7 (Hodogaya chemical industry (strain) system).

Ctube100 (CNT Inc.).

FloTube9000,7000,2000 (above by CNanoTechnology Inc.).

SWNTs99wt%, OHFunctionalized, COOHFunctionalized, NH2Functionalized, 90wt%, COOH, 60wt%, ShortSWNTs90wt%, OH, COOH, 60wt%, DWNTs, MWNTs99wt% < 20nm, 95wt% < 8nmOD, 8-15nmOD, 10-20nmOD, 20-30nmOD, 30-50nm, > 50nmOD, TWNTs (above by CheapTubes Inc.).

Carbon black adopts oven process, channel process, acetylene method, pyrolysis method etc. to make, and the carbon black used in the present invention can be adopt any one method to obtain.

Particularly, following commercially available product etc. can be used.

Raven5000UltraIII, 5000UltraII, 7000,3500,2500Ultra, 1500,1255,1200,1170,1100Ultra, 1060Ultra, 1040,1035,1020, L, 1000,890,850,460,450,420,410,22,16,14, H2O, Conductex975Ultra (above by ColumbianCarbon society system).

#2650, #2600, #2350, #2300, #1000, #980, #970, #960, #950, #900, #850, MCF88, MA600, #750B, #650B, #52, #47, #45, #45L, #44, #40, #33, #32, #30, #25, #20, #10, #5, #95, #85, #260, MA77, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, MA220, MA14, #4000B, #3030B, #3050B, #3230B, #3400B (being made by Mitsubishi Chemical's (strain) above).

Printex95, 90, 85, 80, 75, 60, 60-A, 55, 45, 40, 35, 30, 25, 12, alpha, A, L6, L, P, 140U, 140V, U, V, XE2-B, XE2, ES34, ES23, ES22, F85, F80, Falpha, FP, L6SQ, LSQ, alphaSQ, 300, 200, G, ColorBlackFW200, FW2, FW2V, FW285, FW1, FW18, S170, S160, SpecialBlack550, 350, 250, 100, 6, 5, 4, 4A, Hiblack970LB, 930L, 890, 600L, 40B2, 40L, 45LB, 30L, 30, 20L, 200L, 20, 10, 5L, NIPex180IQ, 170IQ, 160IQ, 150, 90, 70, 60, 35, NEROX600, 605, 510, 505, 305, 5600, 3500, 2500, 1000, LampBlack101, Arosperse15, XPB235 (ORIONENGINEEREDCARBONS company (former Degussa society) system).

Rising sun #8, #15, #22K, #35, #15HS, #50HG, #50U, #51, #52, #60HN, #60U, #66, #70L, AX-015, F-200, AsahiThermal, SUNBLACK900,910,935,960,300,320,700,710,720,805,200,210,220,230,240,250,260,270,280,400,410,600, X15, X25, X45, X55, X65 (rising sun Carbon (strain) system).

Tokablack#8500/F, #8300/F, #7550SB/F, #7400, #7360SB, #7350/F, #7270SB, #7100F, #7050, #5500, #4500, #4400, #4300, #3855, #3845, #3800, ordinary carbon black, Aqua-Black162,001 (East Sea Carbon (strain) system).

Monarch120,280,460,700,800,880,900,1000,1100,1300,1400,2000,4630, Regal99,99R, 415,415R, 250,250R, 330,330R, 400R, 550R, 660R, ValcanXC-72R, BlackPearls480, Pearls130, ELfex-8, MogulL (Cabot society system).

Primary particle size for these carbon blacks is not particularly limited, and is preferably 3 ~ 500nm, is more preferably 10 ~ 100nm, considers the degree of blackness improving carbon black further, more preferably 10 ~ 50nm.

As solvent, as long as carbon material can be formed by dispersed composition, can be just arbitrary solvent, can enumerate such as, water, toluene, p-Xylol, o-Xylol, m-xylene, ethylbenzene, vinylbenzene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, Ethylene Glycol Methyl ether acetic acid ester, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, DPGME, diethylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, carbiphene, triglyme, diethylene glycol monoethyl ether acetate, glycol ether, 1-octanol, ethylene glycol, hexylene glycol, trimethylene, 1-methoxyl group-2-butanols, hexalin, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzylalcohol, 1,3 butylene glycol, BDO, 2,3-butanediol, gamma-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl Ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, cyclopentanone, pimelinketone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methyl alcohol, ethanol, Virahol, the trimethyl carbinol, vinyl carbinol, n-propyl alcohol, 2-methyl-2-butanols, isopropylcarbinol, propyl carbinol, 2-methyl-1-butene alcohol, 1-amylalcohol, 2-methyl-1-pentene alcohol, 2-Ethylhexyl Alcohol, 1-methoxy-2-propanol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-two alkane, N, dinethylformamide, N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, methyl-sulphoxide, CHP etc., they may be used alone, can also be 2 or more kinds in combination.

Solid component concentration for the carbon material in carbon material dispersion membrane formation composition is not particularly limited, and in composition of the present invention, can be about 0.0001 ~ 50 quality %, is preferably about 0.0001 ~ 20 quality %.

As the decentralized processing of carbon material, be not particularly limited, ultrasonication, wet shotcrete technology formula grinding machine, ball mill, ball mill, paint shaker, basket grinding machine, enlightening promise grinding machine (Dyno-mill), super sticky grinding machine, annular dispersion machine etc. can be used.In addition, the carbon material dispersion membrane obtained by them is formed and known filter or separating machine also can be used as required to process with composition.

In composition of the present invention, be not particularly limited for containing the polymkeric substance of triazine ring and the mixture ratio of carbon material, counting in mass ratio, can be about 1000: 1 ~ 1: 100.

In addition, in composition with an organic solvent, containing the concentration of the polymkeric substance of triazine ring, as long as carbon material can be made to be dissolved in concentration in organic solvent, just be not particularly limited, in the present invention, concentration is in the composition preferably about 0.001 ~ 50 quality %, is more preferably about 0.005 ~ 20 quality %.

In carbon material dispersion membrane formation composition of the present invention, only otherwise damage effect of the present invention, also other compositions except the polymkeric substance containing triazine ring, linking agent, carbon material and solvent can be contained, such as, the additive such as flow agent, tensio-active agent, pigment, dyestuff, silane coupling agent.

As tensio-active agent, can enumerate such as, the Voranol EP 2001 classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene cetyl base ether, polyoxyethylene oleyl ether; The polyoxyethylene alkylallyl base ethers such as polyoxethylene octylphenyl phenol ether, polyoxyethylene nonylphenol ether; Polyoxyethylene polyoxypropylene block copolymer class; The sorbitan fatty acid esters classes such as sorbitan monolaurate, span 40, sorbitan monostearate, dehydrated sorbitol mono-fatty acid ester, sorbitan trioleate, sorbitan tristearate; The nonionic surface active agent such as polyoxyethylene sorbitan fatty acid esters class such as Tween 20, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; (Mitsubishi's Materials electronics changes into the fluorine system tensio-active agent such as (strain) system (former (strain) Jemco system), trade(brand)name MegafacF171, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (DIC (strain) system), FluoradFC430, FC431 (Sumitomo 3M (strain) system), trade(brand)name AsahiGuardAG710, SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain) system) for trade(brand)name EftopEF301, EF303, EF352; Organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (BYK-ChemieJapan (strain) system) etc.

These tensio-active agents may be used alone, or two or more kinds may be used in combination.Relative to polymkeric substance 100 mass parts containing triazine ring, the usage quantity of tensio-active agent is preferably 0.0001 ~ 5 mass parts, is more preferably 0.001 ~ 1 mass parts, more preferably 0.01 ~ 0.5 mass parts.

Be explained, above-mentioned other composition can modulate the present composition time any operation in add.

As pigment, can enumerate such as, the carbon such as coal tar, coal-tar pitch series pigments; Titanium is black waits the black inorganic pigment etc. such as titanium oxide base pigment, iron oxide pigment, cupric oxide.As dyestuff, can enumerate such as, black dyes, orchil, yellow dyes, blue dyes etc.

Particularly, following commercially available product etc. can be used.

Titanium is black: 12S, 13M, 13M-C (Mitsubishi Materials (strain) system).

Black dyes: VALIFASTBLACK1807,1821,3804,3810,3820,2830,2840,3866,3870, OilBlack803,830,860, BS, HBB, NO5 (Orient chemical industry (strain) system), AizenSpilonBlackMHS-Liquid (Hodogaya chemical industry (strain) system).

Orchil: VALIFASTRED1308,1320,1355,1360,1364,1388,2320,3108,3304,3306,3311,3312,3320, OILRED330,5B, OG, RR (Orient chemical industry (strain) system), AizenSpilonRedBEHS-Liquid (Hodogaya chemical industry (strain) system).

Yellow dyes: VALIFASTYELLOW1101,1108,1109,1151,1171,3108,3120,3150,3170,3180,4120,4121, OILYELLOW107,129,136,3G, GG-S (Orient chemical industry (strain) system), AizenSpilonYellowRHS-Liquid (Hodogaya chemical industry (strain) system).

Blue dyes: VALIFASTBLUE1063,1605,1621,2606,2620,2650,2670, OILBLUE2N, 613,630,650M (Orient chemical industry (strain) system).

These pigment and dyestuff may be used alone, or two or more kinds may be used in combination.Relative to polymkeric substance 100 mass parts containing triazine ring, the usage quantity of pigment or dyestuff is preferably 0.001 ~ 20 quality %, is more preferably about 0.005 ~ 10 quality %.

Be explained, above-mentioned other composition can modulate composition of the present invention time any operation in add.

Carbon material dispersion membrane formation composition of the present invention can by being coated on base material, then carries out as required after heating makes solvent evaporate, forming desired cured film by heating or rayed.

The coating process of composition is arbitrary, can adopt such as, the method such as spin-coating method, dip coating, flow coat method, ink jet method, injection dotting glue method, spray method, stick coating method, gravure coating process, slot coated method, rolling method, transfer printing, spread coating, scraper plate coating method, air knife coating method.

In addition, as base material, can enumerate and comprise: the base material etc. of silicon, the glass by tin indium oxide (ITO) film forming, the glass by indium zinc oxide (IZO) film forming, polyethylene terephthalate (PET), plastics, glass, quartz, pottery etc., also can use and there is flexible elastic substrate.

About maturing temperature, as long as the object making solvent evaporate can be reached, be just not particularly limited, can carry out at such as 40 ~ 400 DEG C.

As roasting method, be not particularly limited, as long as adopt such as, use hot-plate or baking oven, in the suitable atmosphere that the rare gas element such as air, nitrogen, vacuum are medium, make it evaporate.

Maturing temperature and roasting time can be selected according to the condition of the manufacturing procedure of the electron device of applicable object, or select according to the roasting condition being applicable to making the physics value of obtained film meet the requirement characteristic of electron device.

The condition of carrying out light-struck situation is also not particularly limited, according to the used polymkeric substance containing triazine ring and linking agent, as long as adopt suitable irradiation energy and time.

The cured film of the present invention so obtained is owing to reaching high heat resistance, high refractive index, and low volumetric shrinkage, therefore go at making liquid-crystal display, organic electroluminescent (EL) indicating meter, touch-screen, photosemiconductor (LED) element, solid-state imager, organic thin film solar cell, dye-sensitized solar cell, OTFT (TFT), lens, prism, photographic camera, binocular, microscope, a kind of parts etc. during semiconductor exposure device etc., in electron device or optical material field, in the decoration coating of various parts surfaces etc. or the field of ink.Wherein, the inner face reflection purposes of the lens of photographic camera etc. is suitable for.

Be explained, in order to obtained cured film flatness, prevent the physics of carbon material from coming off, also composition in addition to carbon material in above-mentioned carbon material dispersion membrane formation composition can be made smoothing material, use this smoothing material further stacked planarization film on above-mentioned cured film (carbon material dispersion membrane).

In this smoothing material, same as described above containing the concrete example of the polymkeric substance and linking agent etc. of triazine ring, their use level and film formation method.

Embodiment

Below list synthesis example and embodiment, further illustrate the present invention, but the present invention is not limited to following embodiment.Be explained, each determinator used in embodiment is as follows.

[ ¹H-NMR]

Device: VarianNMRSystem400NB (400MHz)

JEOL-ECA700(700MHz)

Measure solvent: DMSO-d6

Base Quasi material: tetramethylsilane (TMS) (δ 0.0ppm)

[GPC]

Device: Tosoh (strain) HLC-8200GPC processed

Post: ShodexKF-804L+KF-805L

Column temperature: 40 DEG C

Solvent: tetrahydrofuran (THF) (hereinafter abbreviated as THF)

Detector: UV (254nm)

Calibration curve: polystyrene standard

[ellipsometer]

Device: JAWoollamJapan multiple angles of incidence light splitting ellipsometer VASE

[differential thermal Libra (TG-DTA)]

Device: (strain) Rigaku TG-8120

Heat-up rate: 10 DEG C/min

Measure temperature: 25 DEG C-750 DEG C

[turbidometer]

Device: Japanese electric look (strain) NDH5000 processed

[UV, visible light near-infrared absorption spectrum]

Device: (strain) Shimadzu Seisakusho Ltd. UV-3600

[size-grade distribution meter]

Device: day machine dress (strain) MicrotracUPA-EX processed

[viscometer]

Device: eastern machine industry (strain) VISCOMETERTV-22 processed

[1] containing the synthesis of the hyperbranched polymer of triazine ring

The synthesis of [synthesis example 1] HB-TmDA

[changing 17]

In nitrogen, in 1000mL four-hole boiling flask, add DMAc456.02g, be cooled to-10 DEG C with acetone-dry ice bath, add 2,4,6-tri-chloro-1,3,5-triazine [1] (84.83g, 0.460mol, EvonikDegussa society system) makes it dissolve.Then, mphenylenediamine [2] (62.18g, the 0.575mol) and the aniline (14.57g, 0.156mol) that are dissolved in DMAc304.01g is instilled.Stir 30 minutes after instillation, this reaction soln is placed stand-by, in 2000mL four-hole boiling flask, adds DMAc621.85g, this reaction vessel is heated to 85 DEG C with oil bath in advance, then spend within 1 hour, instill above-mentioned reaction soln with fresh feed pump, stir and make it be polymerized in 1 hour.

Then, add aniline (113.95g, 1.224mol), stir after 1 hour and terminate reaction.Be cooled with an ice bath to room temperature, instillation triethylamine (116.36g, 1.15mol), stirs 30 minutes, uses hydrochloric acid chilling.Then, the hydrochloride filtering precipitation is crossed.The reaction soln filtered 28% ammonia soln (279.29g) and the mixing solutions of deionized water (8820g) are carried out redeposition.Throw out is filtered, is again dissolved in THF (833.1g), carries out redeposition with deionized water (6665g) after dry 8 hours with pressure Reduction Dryer at 150 DEG C.Obtained throw out is filtered, with pressure Reduction Dryer at 150 DEG C dry 25 hours, obtains macromolecular compound [3] (being hereafter the abbreviated as HB-TmDA40) 118.0g as target.

HB-TmDA40's ¹the measurement result of H-NMR spectrum is shown in Fig. 1.The HB-TmDA40 obtained is for having the compound of the structural unit represented by formula (1).The weight-average molecular weight Mw by polystyrene conversion of the GPC mensuration of HB-TmDA40 is 4,300, polydispersity Mw/Mn is 3.44.

(1) thermal test

Carry out TG-DTA mensuration to the HB-TmDA40 obtained in synthesis example 1, the temperature that its 5% weight reduces is 419 DEG C.The results are shown in Fig. 2.

(2) detecting refractive index

The HB-TmDA400.5g obtained in synthesis example 1 is dissolved in pimelinketone 4.5g, obtains shallow yellow transparent solution.Used by obtained polymer varnish spin coater with 200rpm spin coating 5 second, with 2000rpm spin coating 30 second on the glass substrate, heat at 150 DEG C 1 minute, at 250 DEG C, heat 5 minutes with except desolventizing, obtain tunicle.Measure obtain the specific refractory power of tunicle, result is the specific refractory power at 550nm place is 1.790.

[preparation example 1]

The HB-TmDA4040g obtained in synthesis example 1 is dissolved in pimelinketone 153.6g and deionized water 6.4g, modulates the solution (hereinafter referred to as HB-TmDA40V) of 20 quality %.

[preparation example 2]

Ethoxylated glycerol triacrylate (hereinafter referred to as NKESTERA-GLY-20E, Xin Zhong village chemical industry (strain) system) 1.0g, ethoxylation tetramethylol methane tetraacrylate (hereinafter referred to as NKESTERATM-35E, Xin Zhong village chemical industry (strain) system) 0.3g are dissolved in pimelinketone 5.0g and deionized water 0.2g, modulate the solution (hereinafter referred to as 20E-35EV) of 20 quality %.

[preparation example 3]

Pimelinketone 480.0g and deionized water 20.0g is mixed, the mixed solvent (hereinafter referred to as CHN/ water) of modulation pimelinketone/deionized water.

The making of [preparation example 4] SWCNT dispersion liquid 1

HB-TmDA40V0.1g and the CHN/ water 39.9g obtained in preparation example 1 is mixed, adds SWCNT (HanwhaNanotech Inc., ASP-100F) 0.01g wherein.B ultrasound irradiating unit (Tokyo nitre apparatus (strain) system, FineFU-6H type) is used at room temperature to carry out 1 hr ultrasonic ripple process, and then with 10,000G carries out (room temperature) centrifugation in 1 hour (miniature high-speed cooling whizzer, (strain) Tomy Seiko SRX-201), obtains the SWCNT dispersion liquid 1 of the black transparent as supernatant liquor.

Measure obtain the UV, visible light near-infrared absorption spectrum of SWCNT dispersion liquid 1, result clearly observes semiconductive S ₁₁band (1,300 ~ 850nm), S ₂₂the absorption of band (850 ~ 600nm) and metallicity band (600 ~ 450nm), confirms that SWCNT is isolated and dissolves (see Fig. 3).

The making of [preparation example 5] SWCNT dispersion liquid 2

Except using 20E-35EV0.1g, all the other modulate SWCNT dispersion liquid 2 similarly to Example 1, and measure UV, visible light near-infrared absorption spectrum, result does not observe the absorption of above-mentioned each band, confirm the bad dispersibility (see Fig. 4) of SWCNT.

The modulation of [embodiment 1] Photocurable composition 1

Add the SWCNT dispersion liquid 120.0g of modulation in preparation example 4,60 quality %A-GLY-20ECHN/ aqueous solution 2mg, 60 quality %ATM-35ECHN/ aqueous solution 1mg and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) CHN/ aqueous solution 0.01g, the varnish (hereinafter referred to as HB-TmDA40VF1) of modulation total solids constituent concentration 0.1 quality %.

The modulation of [comparative example 1] Photocurable composition 2

Except using the SWCNT dispersion liquid 2 of modulation in preparation example 5, all the other modulate the varnish (hereinafter referred to as 20E-35EVF1) of total solids constituent concentration 0.1 quality % similarly to Example 1.

[embodiment 2] photocuring film 1

By the HB-TmDA40VF1 of modulation in embodiment 1 on soda-lime glass substrate with spin coater with 100rpm spin coating 5 second, with 200rpm spin coating 30 second, with hot-plate roasting 3 minutes at 130 DEG C.Then, with high pressure mercury vapour lamp with integration exposure 400mJ/cm ²make it solidify, obtain photocuring film 1.

Measure obtain the UV, visible light near-infrared absorption spectrum of tunicle, result clearly observes semiconductive S ₁₁band (1,300 ~ 850nm), S ₂₂the absorption of band (850 ~ 600nm) and metallicity band (600 ~ 450nm), confirms the isolated dispersion (see Fig. 5) of SWCNT.

In addition, after tunicle is flooded 5 minutes in CHN/ water, dry, again measure UV, visible light near-infrared absorption spectrum, results verification, from the absorption spectrum of SWCNT, confirms that film solidifies (see Fig. 6) thus.

[comparative example 2] photocuring film 2

Except using the 20E-35EVF1 of modulation in comparative example 1, all the other operate similarly to Example 2, obtain photocuring film 2.

Measure institute and obtain the UV, visible light near-infrared absorption spectrum of tunicle, result does not observe the absorption of above-mentioned each band, the bad dispersibility (see Fig. 7) of confirmation SWCNT.

In addition, after tunicle is flooded 5 minutes in CHN/ water, dry, again measure UV, visible light near-infrared absorption spectrum, but the absorption (see Fig. 8) of above-mentioned each band can not be confirmed equally.

The making of [preparation example 6] CB dispersion liquid 1

By obtain in preparation example 1 HB-TmDA40V185.1g, carbon black [Printex95 (ORIONENGINEEREDCARBONS Inc., primary particle size: 15nm, specific surface area: BET-240m ²/ g)] 37.0g, pimelinketone 74.8g, the deionized water 3.1g ball mill [Aimex RBM-08, vessel content: 800ml] being filled with zirconium white [Nikkato society system, YTZBalls, φ 1.0mm] 1160.0g, disperse according to lower 5 minutes of 200rpm, the 1500rpm condition of lower 3 hours, obtain the dispersion liquid (hereinafter referred to as CB dispersion liquid 1) of black.

The making of [preparation example 7] CB dispersion liquid 2

Except use in preparation example 1 obtain HB-TmDA40V144.4g, carbon black [Printex95 (ORIONENGINEEREDCARBONS Inc., primary particle size: 15nm, specific surface area: BET-240m ²/ g)] 28.9g, pimelinketone 121.6g, beyond deionized water 5.1g, all the other operate in the same manner as preparation example 6, obtain dispersion liquid (hereinafter referred to as CB dispersion liquid 2).

[preparation example 8]

The HB-TmDA4040.0g obtained in synthesis example 1 is dissolved in cyclopentanone 153.6g and deionized water 6.4g, modulates the solution (hereinafter referred to as HB-TmDA40V2) of 20 quality %.

The making of [preparation example 9] CB dispersion liquid 3

Except use in preparation example 8 obtain HB-TmDA40V2150.0g, carbon black [NIPex90 (ORIONENGINEEREDCARBONS Inc., primary particle size: 14nm, specific surface area: BET-350m ²/ g)] 30.0g, cyclopentanone 115.2g, beyond deionized water 4.8g, all the other operate in the same manner as preparation example 6, obtain dispersion liquid (hereinafter referred to as CB dispersion liquid 3).

The making of [preparation example 10] CB dispersion liquid 4

Except use in preparation example 8 obtain HB-TmDA40V2150.0g, carbon black [NIPex35 (ORIONENGINEEREDCARBONS Inc., primary particle size: 31nm, specific surface area: BET-60m ²/ g)] 30.0g, cyclopentanone 115.2g, beyond deionized water 4.8g, all the other operate in the same manner as preparation example 6, obtain dispersion liquid (hereinafter referred to as CB dispersion liquid 4).

The making of [preparation example 11] CB dispersion liquid 5

Except use in preparation example 8 obtain HB-TmDA40V2187.5g, carbon black [NIPex35 (ORIONENGINEEREDCARBONS Inc., primary particle size: 31nm, specific surface area: BET-60m ²/ g)] 37.5g, cyclopentanone 81.0g, beyond deionized water 3.4g, all the other operate in the same manner as preparation example 6, obtain dispersion liquid (hereinafter referred to as CB dispersion liquid 5).

The making of [preparation example 12] CB dispersion liquid 6

Replace except HB-TmDA40V2 except using the 20 quality %ATM-35CPN/ aqueous solution 150.0g be mixed to get by ATM-35E40.0g, cyclopentanone (hereinafter referred to as CPN) 153.6g, deionized water 6.4g, all the other operate in the same manner as preparation example 9, obtain dispersion liquid (hereinafter referred to as CB dispersion liquid 6).

Use median size and the viscosity of the CB dispersion liquid 1 ~ 6 obtained in sreen analysis meter and the above-mentioned preparation example 6,7,9 ~ 12 of viscometer determining respectively.There is gelation, according to gelation does not occur with visual being confirmed whether in the storage stability of dispersion liquid: zero, gelation occurs: × benchmark evaluate.Result is shown in table 1.

[table 1]

As shown in table 1, when dispersion agent uses HB-TmDA, confirm that carbon black disperses expeditiously.

[preparation example 13]

Cyclopentanone 192.0g, deionized water 8.0g are mixed, the mixed solvent (hereinafter referred to as CPN/ water) of modulation cyclopentanone/deionized water.

The modulation 3 of [embodiment 3] Photocurable composition

Add 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CHN/ aqueous solution 1.2g, 60 quality %A-GLY-20ECHN/ aqueous solution 4.0g, 60 quality %ATM-35ECHN/ aqueous solution 1.2g, the CB dispersion liquid 1195.5g of modulation in preparation example 6, and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) CHN/ aqueous solution 18.0g, the composition of modulation total solids constituent concentration 25 quality %, by the dispersion liquid syringe filter disk [MillexAP (trade(brand)name) obtained, aperture: 2.0 μm, MILLIPORE Inc.] filter (hereafter this dispersion liquid being called Photocurable composition 3).

The modulation 4 of [embodiment 4] Photocurable composition

Add CB dispersion liquid 2209.5g and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) the CHN/ aqueous solution 15.2g of modulation in 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CHN/ aqueous solution 1.0g, 60 quality %A-GLY-20ECHN/ aqueous solution 3.4g, 60 quality %ATM-35ECHN/ aqueous solution 1.0g, preparation example 7, total solids constituent concentration is made to be 20 quality %, in addition, all the other modulate dispersion liquid (hereafter this dispersion liquid being called Photocurable composition 4) similarly to Example 3.

The modulation 5 of [embodiment 5] Photocurable composition

Add CB dispersion liquid 3210.0g and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) the CPN/ aqueous solution 10.5g of modulation in the CPN/ water 114.5g of modulation in 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CPN/ aqueous solution 1.1g, 60 quality %ATM-35ECPN/ aqueous solution 14.0g, preparation example 13, preparation example 9, total solids constituent concentration is made to be 15 quality %, in addition, all the other modulate dispersion liquid (hereafter this dispersion liquid being called Photocurable composition 5) similarly to Example 3.

The modulation 6 of [embodiment 6] Photocurable composition

Add CB dispersion liquid 4180.0g and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) the CPN/ aqueous solution 9.0g of modulation in the CPN/ water 98.2g of modulation in 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CPN/ aqueous solution 0.9g, 60 quality %ATM-35ECPN/ aqueous solution 12.0g, preparation example 13, preparation example 10, total solids constituent concentration is made to be 15 quality %, in addition, all the other modulate dispersion liquid (hereafter this dispersion liquid being called Photocurable composition 6) similarly to Example 3.

The modulation 7 of [embodiment 7] Photocurable composition

Add CB dispersion liquid 5160.0g and 20 quality % optical free radical initiator IrgacureOXE-02 (BASF AG's system) the CPN/ aqueous solution 10.1g of modulation in the CPN/ water 15.7g of modulation in 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CPN/ aqueous solution 1.0g, 60 quality %ATM-35ECPN/ aqueous solution 13.4g, preparation example 13, preparation example 11, total solids constituent concentration is made to be 25 quality %, in addition, all the other modulate dispersion liquid (hereafter this dispersion liquid being called Photocurable composition 7) similarly to Example 3.

The modulation 8 of [comparative example 3] Photocurable composition

Except using the CB dispersion liquid 6 of modulation in preparation example 12, all the other attempt the dispersion liquid modulating total solids constituent concentration 20 quality % similarly to Example 5, but syringe filter disk [MillexAP (trade(brand)name), aperture: 2.0 μm, MILLIPORE Inc.] is blocked when filtering, therefore, the dispersion liquid (hereafter this dispersion liquid being called Photocurable composition 8) do not filtered below is used.

The modulation 1 of [embodiment 8] thermoset composition

Add the CB dispersion liquid 3109.2g of modulation in the CPN/ water 39.0g of modulation in 1 quality % tensio-active agent MegafacR-40 (DIC (strain) system) CPN/ aqueous solution 0.6g, 50 quality %AcrydicA-817 (DIC (strain) system) CPN/ aqueous solution 1.32g, preparation example 13, preparation example 9, the dispersion liquid of modulation total solids constituent concentration 15 quality %, filters (hereafter this dispersion liquid being called CB dispersion liquid 7) by obtained dispersion liquid syringe filter disk [MillexAP (trade(brand)name), aperture: 2.0 μm, MILLIPORE Inc.].

Then, add Coronate2770 (Nippon Polyurethane Industry (Ltd.)) 22.5g and cyclopentanone 127.5g, in the solution 1.4g filtered with syringe filter disk [MillexAP (trade(brand)name), aperture: 2.0 μm, MILLIPORE Inc.], add the CB dispersion liquid 77.0g of modulation in advance, obtain the thermoset composition (hereafter this dispersion liquid being called thermoset composition 1) of total solids constituent concentration 15 quality %.

By the viscosity of the Photocurable composition 3 ~ 8 obtained in viscometer determining above-described embodiment 3 ~ 8, comparative example 3, thermoset composition 1.Result is shown in table 2.

[table 2]

[embodiment 9] photocuring film 3

By the Photocurable composition 3 of modulation in embodiment 3 on alkali-free glass substrate with spin coater with 200rpm spin coating 5 second, with 700rpm spin coating 30 second, with hot-plate roasting 3 minutes at 130 DEG C.Then, with high pressure mercury vapour lamp with integration exposure 400mJ/cm ²condition make it solidify, make photocuring film 3.

[embodiment 10] photocuring film 4

Except using the Photocurable composition 4 of modulation in embodiment 4, all the other make photocuring film 4 similarly to Example 9.

[embodiment 11] photocuring film 5

Except using the Photocurable composition 5 of modulation in embodiment 5, all the other make photocuring film 5 similarly to Example 9.

[embodiment 12] photocuring film 6

Except using the Photocurable composition 6 of modulation in embodiment 6, all the other make photocuring film 6 similarly to Example 9.

[embodiment 13] photocuring film 7

Except using the Photocurable composition 7 of modulation in embodiment 7, all the other make photocuring film 7 similarly to Example 9.

[comparative example 4] photocuring film 9

Except using the Photocurable composition 8 of modulation in comparative example 3, all the other make photocuring film 9 similarly to Example 9.

[embodiment 14] heat cured film 1

Use the thermoset composition 1 of modulation in embodiment 8, with 200rpm spin coating 5 second, with 700rpm spin coating 30 second, with hot-plate roasting 60 minutes at 120 DEG C, make heat cured film 1.

The total light transmittance of photocuring film 3 ~ the 9 and heat cured film 1 obtained in above-described embodiment 9 ~ 14, comparative example 4 is determined with the measurement of Turbid degree.And then flood the thickness after 3 minutes with after film thickness measuring customised films and in CHN, obtain residual film ratio by the measured value after CHN floods.Result is shown in table 3.

[table 3]

The tunicle obtained in above-described embodiment 9 ~ 14, its total light transmittance is less than 0.1% (0.00% for detecting boundary), obtains the uniform film that opacifying property is high.And then the residual film ratio before and after CHN dipping is more than 94%, confirm that film solidifies.On the other hand, comparative example 4 occurs that radial film is uneven, for surface is in the tunicle of the shape that is clamminess.

Claims

1. carbon material dispersion membrane formation composition, is characterized in that, wherein comprises the polymkeric substance containing triazine ring containing the repeat unit structure represented by following formula (1), linking agent and carbon material:

In formula, R ⁹⁸~ R ¹⁰¹represent the alkoxyl group of the alkyl of the had branched structure of hydrogen atom, halogen atom, carboxyl, sulfo group, carbon number 1 ~ 10 or the had branched structure of carbon number 1 ~ 10 independently of each other; Y ¹and Y ²represent the alkylidene group of the had branched structure of singly-bound or carbon number 1 ~ 10 independently of each other.

2. carbon material dispersion membrane formation composition according to claim 1, wherein, above-mentioned carbon material contains at least a kind that is selected from carbon nanotube, carbon nanohorn, soccerballene, Graphene, carbon black, section's qin carbon black, graphite and carbon fiber.

3. carbon material dispersion membrane formation composition according to claim 1, wherein, above-mentioned carbon material contains carbon nanotube, and this carbon nanotube is isolated is dispersed to individual size.

4. carbon material dispersion membrane formation composition according to claim 1, wherein, above-mentioned carbon material is carbon black.

5. the carbon material dispersion membrane formation composition described in wantonly 1 of Claims 1 to 4, wherein, above-mentioned linking agent is the compound of photocurable and/or thermofixation.

6. the carbon material dispersion membrane formation composition described in wantonly 1 of Claims 1 to 4, wherein, above-mentioned linking agent is be selected from least a kind in multifunctional (methyl) acrylic compounds, multi-functional epoxy compound and polyfunctional isocyanate compound.

7. cured film, it is for obtaining by making carbon material dispersion membrane formation composition described in wantonly 1 of claim 1 ~ 6 solidify.

8. electron device, it cured film according to claim 7 possessing base material and formed on the substrate.

9. optical material, it cured film according to claim 7 possessing base material and formed on the substrate.